CN102764599B - A kind of preparation method of nano material mixed substrate membrane containing nano-grade molecular sieve - Google Patents
A kind of preparation method of nano material mixed substrate membrane containing nano-grade molecular sieve Download PDFInfo
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Abstract
A preparation method for nano material mixed substrate membrane containing nano-grade molecular sieve, comprises two steps: step one, preparation implant the micropore intermediate layer of nano material; Step 2, filter cortex in the micropore interlayer surfaces preparation of implanting nano material, by the present invention, nano material is high in film surface fastness, difficult drop-off in application process, and nano material is even in film surface distributed, not easily assembles; In addition, nano material easily controls in the coverage rate on film surface; Therefore, the function of nano material can be not fully exerted, and does not cause the infringement of membrane filtration characteristic.
Description
Technical field
The present invention relates to a kind of preparing technical field of composite membrane, particularly a kind of preparation method of nano material mixed substrate membrane containing nano-grade molecular sieve.
Background technology
The high-pressure membrane such as reverse osmosis membrane and NF membrane has extensive and irreplaceable application at the numerous areas such as drinking water treatment and reusing sewage.Owing to having higher membrane flux and the rejection high to dissolved organic matter, composite membrane is the main form of current high-pressure membrane.Composite membrane becomes professional standard prepared by high-pressure membrane substantially.
The architectural feature of composite membrane is: the filtration cortex of passive micropore intermediate layer and filtration is prepared separately, namely first prepares micropore intermediate layer, and cortex is filtered in preparation subsequently.
The same with all membrane filtration processes, composite membrane filters also can be subject to having a strong impact on of fouling membrane.Fouling membrane not only can increase resistance of membrane filtration, reduces membrane flux, also can increase filtration channel resistance, increases operation energy consumption.In addition, fouling membrane also can reduce the interception capacity of film to polluter, worsens effluent quality.
Practice shows, biological pollution is the main form of expression that composite membrane pollutes.Biological pollution shows as the excessive multiplication of microorganism in membrane module.For composite membrane, biological pollution can not by simply adding disinfectant (as Cl
2) mode eliminate.Most composite membrane is all very low to the tolerance of disinfectant.Under the decontaminant concentration of denier, composite membrane can destroy, and has a strong impact on the interception capacity of composite membrane.
Develop the important directions that the composite membrane with antibacterial ability becomes the development of current composite membrane.To implant the Typical Representative that nano material mixed substrate membrane containing nano-grade molecular sieve that inorganic nano material is feature is antibiotic property composite membrane.The high filtration flux of the anti-microbial property of nano material and composite membrane, high pollution thing rejection ideally combine by nano material mixed substrate membrane containing nano-grade molecular sieve.
The current method preparing nano material mixed substrate membrane containing nano-grade molecular sieve mainly contains two kinds.Be existing preparation method one as shown in Figure 1: after composite membrane is formed, then implant nano material at composite film surface.The major defect of this method is that the fastness of nano material on film surface is not high.In mixed substrate membrane containing nano-grade molecular sieve application process, nano material can constantly run off, and the anti-microbial property of mixed substrate membrane containing nano-grade molecular sieve is also along with disappearance.Existing preparation method two as shown in Figure 2: in the reactant solution preparing composite membrane (i.e. mixed substrate membrane containing nano-grade molecular sieve), add nano material.The implantation of nano material and the formation of composite membrane occur simultaneously.The major defect of this method is that nano material is easily assembled, and causes adverse effect to the filtration of mixed substrate membrane containing nano-grade molecular sieve and cutoff performance; Meanwhile, the coverage rate of nano material on film surface is also wayward.
Therefore, be badly in need of the preparation method of a kind of mixed substrate membrane containing nano-grade molecular sieve of exploitation, nano material easily controls in the distribution of film surface uniform, the high and coverage rate of fastness to utilize the method to ensure.
Summary of the invention
In order to solve the problems of the technologies described above, the object of the present invention is to provide a kind of preparation method of nano material mixed substrate membrane containing nano-grade molecular sieve, the nano material mixed substrate membrane containing nano-grade molecular sieve of preparation, its nano material fastness be high, be evenly distributed and coverage rate easily controls.
In order to achieve the above object, technical scheme of the present invention is achieved in that
A preparation method for nano material mixed substrate membrane containing nano-grade molecular sieve, is characterized in that, comprises two steps:
Step one, preparation implant the micropore intermediate layer of nano material;
Step 2, implanting nano material micropore interlayer surfaces preparation filter cortex.
Described nano material comprise in aluminium oxide, titanium dioxide, zirconia, silica, silver, CNT or zeolite one or more.
The average grain diameter of described nano material is between 0.01-1 micron.
The average grain diameter of described nano material is between 0.01-0.2 micron.
Described micropore intermediate layer comprises high-molecular organic material, high-molecular organic material comprise in polysulfones PSf, polyether sulfone PES, polyvinylidene fluoride PVDF, polyvinylchloride, polyacrylonitrile (PAN), polyamide PA, polyimides PI, PEI PEI and copolymer thereof one or more.
Described step one is, preparing micropore intermediate layer while, nano material in-situ is implanted micropore interlayer surfaces.
Described step one first prepares micropore intermediate layer, afterwards nanomaterial solution is spread evenly across micropore interlayer surfaces and realizes implanting.
Described step one first prepares micropore intermediate layer, nano material utilized electrostatic interaction to be adsorbed in micropore interlayer surfaces afterwards and realize implanting.
Described step one first prepares micropore intermediate layer, afterwards nano material is directly injected into micropore interlayer surfaces and realizes implanting.
The average pore size in micropore intermediate layer is between 0.005-1 micron.
The average pore size in micropore intermediate layer is between 0.01-0.5 micron.
The average pore size in micropore intermediate layer is between 0.01-0.1 micron.
The thickness in described micropore intermediate layer is between 10-1000 micron.
The thickness in micropore intermediate layer is between 10-500 micron.
The thickness in micropore intermediate layer is between 10-100 micron.
Described filtration cortex is single or multiple lift.
Described filtration cortex is individual layer, and chemical composition is polyamide, and adopt interfacial polymerization to synthesize, concrete steps are as follows:
The aqueous solution of preparation polyamide precursor thing-polyamines, in polyamines solution, the mass percent concentration of p-phenylenediamine (PPD) MPD is 2%, and the mass percent concentration of triethylamine TEA is 2%, and the mass percent concentration of camphorsulfonic acid CSA is 4%; Prepare the hexane solution of polyamide precursor thing-acyl chlorides again, the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.1%; When cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, again micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, formed and filter cortex, the THICKNESS CONTROL of final filtration cortex is being less than 100 nanometers.
Described filtration cortex is individual layer, and chemical composition is polypiperazine-amide, and adopt interfacial polymerization to synthesize, concrete steps are as follows:
The aqueous solution of preparation polypiperazine-amide precursor-piperazine, wherein containing the piperazine of mass percent 1% and the NaOH of mass percent 0.2%, the cyclohexane solution of preparation polyamide precursor thing-acyl chlorides, wherein the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.13%; When cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, again micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, formed and filter cortex, the THICKNESS CONTROL of final filtration cortex is being less than 100 nanometers.
Described filtration cortex is double-deck, and chemical composition is respectively polypiperazine-amide and polyamide from the inside to the outside, and adopt interfacial polymerization to synthesize, concrete steps are as follows:
First prepare polypiperazine-amide and filter cortex, the aqueous solution of preparation polypiperazine-amide precursor-piperazine, wherein containing the piperazine of mass percent 1% and the NaOH of mass percent 0.2%, the cyclohexane solution of preparation polyamide precursor thing-acyl chlorides, wherein the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.13%, when cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, again micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, formed and filter cortex, the thickness controlling polypiperazine-amide filtration cortex is about 50 nanometers,
Prepare polyamide subsequently and filter cortex, the aqueous solution of preparation polyamide precursor thing-polyamines, in polyamines solution, the mass percent concentration of p-phenylenediamine (PPD) MPD is 2%, the mass percent concentration of triethylamine TEA is 2%, and the mass percent concentration of camphorsulfonic acid CSA is 4%; The hexane solution of preparation polyamide precursor thing-acyl chlorides, the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.1%, when cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, again micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, form polyamide and filter cortex.The thickness controlling polyamide filtration cortex is about 50 nanometers.
By the present invention, nano material is high in film surface fastness, difficult drop-off in application process, and nano material is even in film surface distributed, not easily assembles.In addition, nano material easily controls in the coverage rate on film surface.Therefore, the function of nano material can be not fully exerted, and does not cause the infringement of membrane filtration characteristic.
Accompanying drawing explanation
Fig. 1 is the prior art schematic diagram of nano material mixed substrate membrane containing nano-grade molecular sieve.
Fig. 2 is the prior art schematic diagram of nano material mixed substrate membrane containing nano-grade molecular sieve.
Fig. 3 is the schematic diagram of embodiment one.
Fig. 4 is the schematic diagram of embodiment two.
Fig. 5 is the schematic diagram of embodiment three.
Detailed description of the invention
The preparation method of the nano material mixed substrate membrane containing nano-grade molecular sieve that the embodiment of the present invention provides, can make nano material in mixed substrate membrane containing nano-grade molecular sieve surface distributed evenly, difficult drop-off and coverage rate easily control.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment one
With reference to Fig. 3, the preparation method of the present embodiment, comprises two steps:
Step one, preparation implant the micropore intermediate layer of nano material:
Described nano material is aluminium oxide.
Nano material in described step one adopts " original position implantation " method that nano material is implanted micropore interlayer surfaces at the method for implantation of micropore interlayer surfaces while preparing micropore intermediate layer;
Described micropore intermediate layer material is polysulfones PSf, and mean particle size is 100 nanometers.
Step 2, implanting nano material micropore interlayer surfaces preparation filter cortex.
Described " original position implantation " method is: the surface of nano material in-situ being implanted micropore intermediate layer while preparing micropore intermediate layer, realizes by phase separation method NIPS.Be embodied as in the present embodiment:
The polysulfones of 18 grams is dissolved in 82 grams of 1-METHYLPYRROLIDONE NMP, forms casting solution; Before film forming, be uniformly coated on by casting solution in non-woven polyester fabrics, thickness is 100 microns; Non-solvent is the water containing mass ratio 0.15% nano aluminium oxide mutually, and temperature is 20 ° of C; The non-woven polyester fabrics being coated with casting solution is positioned over non-solvent mutually in, nano aluminium oxide is implanted in the micropore intermediate layer through being separated formed.
A step can realize the preparation in micropore intermediate layer of implanting nano material by " original position implantation " method, and by non-solvent mutually in physical action between nano material and micropore intermediate layer, nano material is more securely embedded in micropore intermediate layer.
In the present embodiment, the average pore size in micropore intermediate layer is between 0.01-0.1 micron.
In the present embodiment, nano aluminium oxide is about 15% in the coverage rate of micropore interlayer surfaces.
Described filtration cortex is individual layer, and chemical composition is polyamide.
The synthesis of described filtration cortex adopts interfacial polymerization to be embodied as in the present embodiment: the aqueous solution of preparation polyamide precursor thing-polyamines: in polyamines solution, the mass percent concentration of p-phenylenediamine (PPD) MPD is 2%, the mass percent concentration of triethylamine TEA is 2%, and the mass percent concentration of camphorsulfonic acid CSA is 4%; The hexane solution of preparation polyamide precursor thing-acyl chlorides, the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.1%; When cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, then micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, formed and filter cortex.The THICKNESS CONTROL of final filtration cortex is being less than 100 nanometers.
The embodiment of the present invention represents the ordinary circumstance of mixed-matrix reverse osmosis membrane, namely filters that cortex is polyamide, nano particle is spherical.
With reference to Fig. 3, compared with method shown in Fig. 1 is existing, the nano material fastness on mixed substrate membrane containing nano-grade molecular sieve surface prepared by method shown in this figure is high; Compared with method shown in Fig. 1, the nano material on mixed substrate membrane containing nano-grade molecular sieve surface prepared by method shown in this figure is evenly distributed, and coverage rate easily controls.
Embodiment two
With reference to Fig. 4, the preparation method of the present embodiment, comprises two steps:
Step one, preparation implant the micropore intermediate layer of nano material;
Adopt " phase separation method NIPS " to prepare micropore intermediate layer, adopt " Physical applications method " that nano material is implanted micropore interlayer surfaces subsequently;
Described micropore intermediate layer material is PEI PEI, and described nano material is CNT, and CNT average length is 200 nanometers, and average diameter is 1 nanometer.
Described " the phase separation method " of preparing micropore intermediate layer is embodied as in the present embodiment: be dissolved in by the PEI of 18 grams in 82 grams of dimethyl formamide DMF, forms casting solution; Before film forming, be uniformly coated on by casting solution in non-woven polyester fabrics, thickness is 100 microns; Non-solvent is water mutually, and temperature is 20 ° of C.The non-woven polyester fabrics being coated with casting solution is positioned over non-solvent mutually in.
In the present embodiment, the average pore size in micropore intermediate layer is between 0.01-0.1 micron.
" Physical applications method " in the present embodiment is embodied as, and by the aqueous suspension of the CNT of 1 milliliter of mass ratio 0.01%, is spread evenly across the above-mentioned micropore interlayer surfaces of 1 square decimeter, stand-by after moisture evaporation.
In the present embodiment, CNT is about 20% in the coverage rate of micropore interlayer surfaces.
Step 2, implanting nano material micropore interlayer surfaces preparation filter cortex.
Described filtration cortex is individual layer, and chemical composition is polypiperazine-amide.
The synthesis of described filtration cortex adopts interfacial polymerization to be embodied as: the aqueous solution of preparation polypiperazine-amide precursor-piperazine, wherein containing the piperazine of mass percent 1% and the NaOH of mass percent 0.2%; The cyclohexane solution of preparation polyamide precursor thing-acyl chlorides, wherein the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.13%.When cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, then micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, formed and filter cortex.The THICKNESS CONTROL of final filtration cortex is being less than 100 nanometers.
The embodiment of the present invention represents a kind of special circumstances of mixed-matrix NF membrane, and namely filtering cortex is still polypiperazine-amide, but selected nano particle-CNT has inner microchannel, is conducive to improving discharge capacity.
With reference to Fig. 4, compared with method shown in Fig. 1, the nano material fastness on mixed substrate membrane containing nano-grade molecular sieve surface prepared by method shown in this figure is high; Compared with method shown in Fig. 1, the nano material on mixed substrate membrane containing nano-grade molecular sieve surface prepared by method shown in this figure is evenly distributed, and coverage rate easily controls.Notice that CNT itself is easily assembled.
Embodiment three
With reference to Fig. 5, the preparation method of the present embodiment, comprises two steps:
Step one, preparation implant the micropore intermediate layer of nano material;
While preparing micropore intermediate layer, adopt " original position implantation " method that nano material is implanted micropore interlayer surfaces;
Described micropore intermediate layer material is polysulfones PSf, and described nano material is zeolite, and mean particle size is 100 nanometers.
Described micropore intermediate layer is prepared by phase separation method NIPS: be dissolved in by the polysulfones of 18 grams in 82 grams of 1-METHYLPYRROLIDONE NMP, forms casting solution; Before film forming, be uniformly coated on by casting solution in non-woven polyester fabrics, thickness is 100 microns; Non-solvent is the water containing mass ratio 0.15% nano zeolite particle mutually, and temperature is 20 ° of C; The non-woven polyester fabrics being coated with casting solution is positioned over non-solvent mutually in, nano zeolite is implanted in the micropore intermediate layer through being separated formed.
In the present embodiment, the average pore size in micropore intermediate layer is between 0.01-0.1 micron.
In the present embodiment, nano zeolite particle is about 15% in the coverage rate of micropore interlayer surfaces.
Step 2, implanting nano material micropore interlayer surfaces preparation filter cortex.
Described filtration cortex is two-layer, and the every one deck namely filtering cortex synthesizes separately.Chemical composition is respectively polypiperazine-amide and polyamide from the inside to the outside.
The synthesis of described filtration cortex adopts interfacial polymerization.
First prepare polypiperazine-amide and filter cortex: the aqueous solution of preparation polypiperazine-amide precursor-piperazine, wherein containing the piperazine of mass percent 1% and the NaOH of mass percent 0.2%; The cyclohexane solution of preparation polyamide precursor thing-acyl chlorides, wherein the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.13%; When cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, then micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, formed and filter cortex.The thickness controlling polypiperazine-amide filtration cortex is about 50 nanometers.
Prepare polyamide subsequently and filter cortex: the aqueous solution of preparation polyamide precursor thing-polyamines, in polyamines solution, the mass percent concentration of p-phenylenediamine (PPD) MPD is 2%, and the mass percent concentration of triethylamine TEA is 2%, and the mass percent concentration of camphorsulfonic acid CSA is 4%; The hexane solution of preparation polyamide precursor thing-acyl chlorides.The mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.1%; When cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, then micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, form polyamide and filter cortex.The thickness controlling polyamide filtration cortex is about 50 nanometers.
With reference to Fig. 5, compared with method shown in Fig. 1, the nano material fastness on mixed substrate membrane containing nano-grade molecular sieve surface prepared by method shown in this figure is high; Compared with method shown in Fig. 1, the nano material on mixed substrate membrane containing nano-grade molecular sieve surface prepared by method shown in this figure is evenly distributed, and coverage rate easily controls.With the main distinction of embodiment one Fig. 3, this figure is that filtering cortex is made up of two-layer, bottom discharge capacity is comparatively strong, and top layer plays main crown_interception)
The embodiment of the present invention represents a kind of special circumstances of mixed-matrix reverse osmosis membrane, and namely selected nano particle-zeolite has internal poles microchannel, is conducive to the discharge capacity improving reverse osmosis membrane.Meanwhile, filter cortex and be made up of two-layer, interior layer is polypiperazine-amide, and water permeable ability is strong, and skin is polyamide, plays real crown_interception.
Claims (15)
1. a preparation method for nano material mixed substrate membrane containing nano-grade molecular sieve, is characterized in that, comprises two steps:
Step one, preparation implant the micropore intermediate layer of nano material;
Step 2, implanting nano material micropore interlayer surfaces preparation filter cortex, the thickness of described filtration cortex is less than the average grain diameter of nano material;
Described step one be by phase separation method preparing micropore intermediate layer while by non-solvent mutually in nano material in-situ implant micropore interlayer surfaces.
2. the preparation method of a kind of nano material mixed substrate membrane containing nano-grade molecular sieve according to claim 1, is characterized in that, described nano material comprise in aluminium oxide, titanium dioxide, zirconia, silica, silver, CNT or zeolite one or more.
3. the preparation method of a kind of nano material mixed substrate membrane containing nano-grade molecular sieve according to claim 1, is characterized in that, the average grain diameter of described nano material is between 0.01-1 micron.
4. according to the preparation method of a kind of nano material mixed substrate membrane containing nano-grade molecular sieve according to claim 1, it is characterized in that, the average grain diameter of described nano material is between 0.01-0.2 micron.
5. the preparation method of a kind of nano material mixed substrate membrane containing nano-grade molecular sieve according to claim 1, it is characterized in that, described micropore intermediate layer comprises high-molecular organic material, high-molecular organic material comprise in polysulfones PSF, polyether sulfone PES, polyvinylidene fluoride PVDF, polyvinylchloride, polyacrylonitrile (PAN), polyamide PA, polyimides PI, PEI PEI and copolymer thereof one or more.
6. the preparation method of a kind of nano material mixed substrate membrane containing nano-grade molecular sieve according to claim 1, is characterized in that, the average pore size in micropore intermediate layer is between 0.005-1 micron.
7. the preparation method of a kind of nano material mixed substrate membrane containing nano-grade molecular sieve according to claim 1, is characterized in that, the average pore size in micropore intermediate layer is between 0.01-0.5 micron.
8. the preparation method of a kind of nano material mixed substrate membrane containing nano-grade molecular sieve according to claim 1, is characterized in that, the average pore size in micropore intermediate layer is between 0.01-0.1 micron.
9. the preparation method of a kind of nano material mixed substrate membrane containing nano-grade molecular sieve according to claim 1, is characterized in that, the thickness in described micropore intermediate layer is between 10-1000 micron.
10. the preparation method of a kind of nano material mixed substrate membrane containing nano-grade molecular sieve according to claim 1, is characterized in that, the thickness in micropore intermediate layer is between 10-500 micron.
The preparation method of 11. a kind of nano material mixed substrate membrane containing nano-grade molecular sieves according to claim 1, it is characterized in that, the thickness in micropore intermediate layer is between 10-100 micron.
The preparation method of 12. a kind of nano material mixed substrate membrane containing nano-grade molecular sieves according to claim 1, it is characterized in that, described filtration cortex is single or multiple lift.
The preparation method of 13. a kind of nano material mixed substrate membrane containing nano-grade molecular sieves according to claim 1, it is characterized in that, described filtration cortex is individual layer, and chemical composition is polyamide, and adopt interfacial polymerization to synthesize, concrete steps are as follows:
The aqueous solution of preparation polyamide precursor thing-polyamines, in polyamines solution, the mass percent concentration of p-phenylenediamine (PPD) MPD is 2%, and the mass percent concentration of triethylamine TEA is 2%, and the mass percent concentration of camphorsulfonic acid CSA is 4%; Prepare the hexane solution of polyamide precursor thing-acyl chlorides again, the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.1%; When cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, again micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, formed and filter cortex, the THICKNESS CONTROL of final filtration cortex is being less than 100 nanometers.
The preparation method of 14. a kind of nano material mixed substrate membrane containing nano-grade molecular sieves according to claim 1, it is characterized in that, described filtration cortex is individual layer, and chemical composition is polypiperazine-amide, and adopt interfacial polymerization to synthesize, concrete steps are as follows:
The aqueous solution of preparation polypiperazine-amide precursor-piperazine, wherein containing the piperazine of mass percent 1% and the NaOH of mass percent 0.2%, the cyclohexane solution of preparation polyamide precursor thing-acyl chlorides, wherein the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.13%; When cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, again micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, formed and filter cortex, the THICKNESS CONTROL of final filtration cortex is being less than 100 nanometers.
The preparation method of 15. a kind of nano material mixed substrate membrane containing nano-grade molecular sieves according to claim 1, it is characterized in that, described filtration cortex is double-deck, and chemical composition is respectively polypiperazine-amide and polyamide from the inside to the outside, adopt interfacial polymerization to synthesize, concrete steps are as follows:
First prepare polypiperazine-amide and filter cortex, the aqueous solution of preparation polypiperazine-amide precursor-piperazine, wherein containing the piperazine of mass percent 1% and the NaOH of mass percent 0.2%, the cyclohexane solution of preparation polyamide precursor thing-acyl chlorides, wherein the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.13%, when cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, again micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, formed and filter cortex, the thickness controlling polypiperazine-amide filtration cortex is 50 nanometers,
Prepare polyamide subsequently and filter cortex, the aqueous solution of preparation polyamide precursor thing-polyamines, in polyamines solution, the mass percent concentration of p-phenylenediamine (PPD) MPD is 2%, the mass percent concentration of triethylamine TEA is 2%, the mass percent concentration of camphorsulfonic acid CSA is 4%, the hexane solution of preparation polyamide precursor thing-acyl chlorides, the mass percent concentration of pyromellitic trimethylsilyl chloride TMC is 0.1%, when cortex is filtered in preparation, polyamines solvent is applied in micropore interlayer surfaces, again micropore intermediate layer is placed in the hexane solution of pyromellitic trimethylsilyl chloride TMC, now form interface between polar solvent and non-polar solution, simultaneously at interface polymerization reaction take place, form polyamide and filter cortex, the thickness controlling polyamide filtration cortex is 50 nanometers.
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| CN102258948A (en) * | 2011-05-31 | 2011-11-30 | 南京帝膜净水材料开发有限公司 | Method for preparing polyamide reverse osmosis compound membrane |
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| JPH09136022A (en) * | 1995-11-10 | 1997-05-27 | Toyota Central Res & Dev Lab Inc | Nonaqueous organic liquid filtering membrane and manufacture therefor and filtering method for nonaqueous organic liquid |
| US20090277837A1 (en) * | 2008-05-06 | 2009-11-12 | Chunqing Liu | Fluoropolymer Coated Membranes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101524626A (en) * | 2008-03-07 | 2009-09-09 | 浙江欧美环境工程有限公司 | External pressure type hollow fiber nano filtering film and preparation method thereof |
| CN101569836A (en) * | 2009-03-27 | 2009-11-04 | 上海应用技术学院 | High-flux composite reverse osmosis membrane and preparation method thereof |
| CN102258948A (en) * | 2011-05-31 | 2011-11-30 | 南京帝膜净水材料开发有限公司 | Method for preparing polyamide reverse osmosis compound membrane |
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